Silyl-azidoformates

ABSTRACT

DISCLOSED ARE NITROGEN CONTAINING SILANE COMPOUNDS OF THE FORMULA   (X)A-SI(-(T)B)-(R-(O-C(=O)-N3)C)D   WHERE R IS AN ORGANIC RADICAL, X IS SELECTED FROM HALO, HYDROXY, ALKOXY, ARYLOXY, ORGANO OXYCARBONYL, AZIDO, AMINE, AND AMIDE RADICALS; T IS SELECTED FROM ALKYL, CYCLOALKYL, ARYL, ALKARYL, AND ARALKYL RADICALS; A IS AN INTEGER FROM 1 TO 3; B IS AN INTEGER FROM 0 TO 2; C IS AN INTEGER FROM 1 TO 10; D IS AN INTEGER FROM 1 TO 3; AND A+B+D EQUALS 4;   -OOC-C(-R&#39;&#39;)-N2, -OOC-N3, AND -SO2-N3   WHERE R&#39;&#39; IS SELECTED FROM HYDROGEN, ALKYL, CYCLOALKYL, ARYL AND -COOR&#34; RADICALS; WHERE R&#34; IS SELECTED FROM ALKYL, CYCLOALKYL, AND ARYL RADICALS.

United States Patent 6 3,705,911 SILYL-AZIDOFORMATES J. Brent Thomson,Wilmington, Del., assignor to Hercules Incorporated, Wilmington, Del.

No Drawing. Application Sept. 30, 1969, Ser. No. 862,531, which is acontinuation-in-part of application Ser. No. 789,974, Dec. 31, 1968.Divided and this application Nov. 16, 1971, Ser. No. 199,300

Int. Cl. C07c 117/00; C07d 109/00 US. Cl. 260-349 Claims ABSTRACT OF THEDISCLOSURE Disclosed are nitrogen containing silane compounds of theformula This is a division of application Ser. No. 862,531, filed Sept.30, 1964, which in turn is a continuation-in-part of copendingapplication Ser. No. 789,974, filed Dec. 31, 1968.

This invention relates to a new class of organic compounds. Thisinvention further relates to a method of improving the adhesion ofpolymers to siliceous materials, metals, metal oxides and in adheringone polymer to another by use of the new organic compounds and to theproducts so produced.

It is known in the art to coat various substrates with polymers.However, in many cases the bond between the polymer and the substrate isweak. In still other cases the adhesion is almost completely lost whenthe polymer coated article is subjected to moist conditions.

It has now been found that the adhesion of any polymer to siliceousmaterials, metals, metal oxides or other polymer substrates can begreatly improved #by the treatment of the substrate with a nitrogencontaining silane compound having the general formula where R is anorganic radical;-X is selected from halo, hydroxy, alkoxy, aryloxy,organo oxycarbonyl, azido, amine, and amide radicals; T is selected fromalkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals; a is an integerfrom 1 to 3; b is an integer from to 2; c is an integer from 1 to d isan integer from 1 to 3; and a+b+d equals 4; and Z is selected from )1 lII where R' is selected from hydrogen, alkyl, cycloalkyl, aryl, and-COOR" radicals; where R" is selected from alkyl, cycloalkyl and arylradicals. Not only does the treatment in accordance with this inventionincrease the adhesion of the polymer to the substrate, it also greatlyimproves wet strength retention.

3,705,911 Patented Dec. 12, 1972 ice Any polymer can be bonded to asiliceous material, metal, metal oxide or another polymer with saidsilane compound in accordance with this invention. Exemplary .of thepolymers which can be so bonded are the hydrocarbon polymers includingsaturated, unsaturated, linear, atactic, crystalline or nonlinearamorphous polymers, copolymers, terpolymers, etc. as for examplepolyethylene, polypropylene, poly(4-methylpentene-1), polybutene-l,polystyrene, styrene-butadiene rubber, butyl rubber, natural rubber,polybutadiene, polyisobutylene, ethylene-propylene copolymer,cis-1,4-polyisoprene, ethylene-propylene-dicyclopentadiene terpolymer,etc. and blends of these polymers with each other. In addition,nonhydrocarbon polymers including the cellulose esters such as celluloseacetate butyrate, acetate rayon, cellulose partial alkyl ethers such ashydroxyethyl and hydroxypropyl cellulose; viscose rayon; polyesters suchas poly(ethylene terephthalate), drying and nondrying alkyd resins,etc., poly- (alkylene oxides) such as poly(ethylene oxide) and poly-(propyleneoxide), etc. poly(arylene oxides) such as poly- (phenyleneoxide), etc.; the polyamides such as nylon, perlon-L, etc. andpoly(vinyl alkyl ethers) such as poly- (vinyl methyl ether), etc.; vinylchloride polymers containing at least 10 mole percent of vinyl chloridesuch as poly(vinyl chloride), vinyl chloride-vinyl acetate copolymers,vinyl chloride-vinylidene chloride copolymers, vinyl chloride-male'icanhydride copolymers, vinyl chloridefumaric acid copolymers, vinylchloride-vinyl acetal copolymers such as the vinyl chloride-vinylbutyral copolymers, vinyl chloride-vinylidene chloride-acrylonitrileterpolymers, vinyl chloride-vinyl acetate-maleic anhydride terpolymersetc.; chlorinated natural rubber; ethylenevinyl acetate copolymers;poly(vinylidene chloride); vinylidene chloride-acrylonitrile copolymers;poly(ethyl acrylate); poly(ethyl methacrylate); polysulfone; epoxyresins; poly [3,3-bis(chloromethyl)oxetane]; polychloroprene;butadiene-acrylonitri'le copolymers; butadiene acrylonitrile-styreneterpolymers; etc. can be bonded to the above-mentioned materials.

The materials or substrates to which the polymers may be bonded, asstated above, include siliceous materials such as glass, asbestos, sand,clay, concrete, stone, brick, ceramic materials, etc.; metals such asaluminum, cadmium, chromium, copper magnesium, nickel, silver, tin,titanium, zinc, etc. and alloys of the metals such as brass, bronze,steel, nickel chrome, etc.; and including metals which have been surfacetreated with phosphates, chromates, etc.; metal oxides such as aluminumoxide, iron oxides, lead oxides, titanium dioxide, zinc oxide, etc.; andother polymers. By the term other polymers is meant any polymer otherthan the polymer which is to be bonded. These materials to which thepolymers may be bonded can be in various forms such as sheets, plates,blocks, wires, cloth, fibers, particles, powders, etc. For example, inaccordance with this invention a polymer can be bonded to glass fibers,cord, plates, or cloth, as-

- bestos sheets or fibers, siliceous fillers such a silicon dioxide(sand) or clay, metal sheets, plates or wires, metal oxide pigments,polymer sheets, woven fabric, fibers, etc.

The process of this invention can be carried out in various ways. Forexample the material or substrate can be coated with a solution of thesilane compound and allowed to dry thus inducing bonding through thesilyl group. {X polymer can be bonded to the thus treated material atthe decomposition temperature of the azide or diazo group. By anothermethod the silane compound and polymer can be deposited together on thematerial and then heated to the decomposition temperature of the azideor diazo group. By still another method a polymer can be treated withthe silane compound so as to react the azide or diazo functional groupunder conditions such that silane condensations do not occur.Subsequently the material or substrate can be contacted with the .thustreated polymer so that coupling occurs through the silyl group. Nomatter which method is used it will be necessary, in accordance withthis invention, to heat the silane compound to initiate the bondingreaction through the azide or diazo group. The temperature at whichbonding is effected can be varied over a wide range depending upon thespecific silane compound employed. In general, however, the temperaturewill be in the range of from about 70 C. to about 350 C. Various amountsof silane compound can be used depending upon the specific compound, thesurface area to be covered, the polymer to be bonded to the material,etc. In general the silane compound will be employed in the form of asolution which can be sprayed, brushed, or poured over the surface ofthe material. Alternatively, the material or substrate can be dippedinto a solution or emulsion of the silane compound. These new compoundsare generally soluble in solvents such as methylene chloride,ethylenedichloride, trichloroethylene, perchloroethylene, methanol,ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, benzene,toluene, etc. and will generally be used in concentrations of from about0.01% to about 20.0% more preferably from about 0.05% to about 5.0% byweight.

In one modification of this invention the nitrogen con? taining silanecompounds can be used to bond various types of reinforcing materials,such as fibers, yarn, cord, fabric, and the like to polymer (rubber)stock. A typical example of bonding reinforcing material is the bondingof poly(ethylene terephthalate) tire cord to rubber tire stock. The saidpolyester tire cord is first treated with the silane compound. This canbe accomplished by contacting the cord with a nitrogen containing silanecompound as for example, by dipping, spraying, brushing, or running itover a coated roll with a solution or dispersion of the silane compoundin a suitable liquid. In the next step the thus treated cord is heatedto a temperature sufiicient to decompose the azide or diazo functionalgroup. In so doing, it is believed the azide or diazo group reacts withthe polyester leaving the silyl group free for later reaction. Next, thetreated cord may be dipped in a standard industrial coating (adhesive)which is compatible with the rubber in which the cord is to be embedded.The coating is a conventional tire cord adhesive essentially comprisinga mixture of a phenol-aldehyde resin and a rubber latex. If desired, thedip in the conventional tire cord adhesive can be omitted with aproportionate decrease in adhesive strength. Finally, the thus treatedtire cord is embedded in a commercial vulcanizable tire stock and cured.While polyester tire cord is recited above, various other syntheticfibers, cords, fabrics, and the like can be bonded to rubber stock inaccordance with this invention. Such other reinforcing materials includepolyolefin, polyamide, poly carbonate, rayon and glass fibers, cords,fabrics and the like. In the case of bonding glass reinforcing materialto rubber tire stock, the heat treatment following the contacting with anitrogen containing silane compound (described above) may not berequired because it is believed the silyl groups react with the glassleaving the amide or diazo functional groups free for later reaction.

In another modification of this invention, metal objects such as metalcans can be treated with a solution of the silane compound, coated witha polymer latex or dispersion and then heated to form a tightly bonded,impervious coating. It will be readily apparent to those skilled in theart that the process of this invention lends itself to any occurrencewhere polymers are to be bonded to siliceous materials, metals, metaloxides or other polymers.

In addition to the above modification of this invention, the nitrogencontaining silane compounds can be used to cross-link polymers.Cross-linking can be carried out by merely admixing the polymer with asmall amount of silane compound and any well known basic or acidiccondensation catalyst. Typical of such catalysts are hydrochloric acid,hydrobromic acid, acetic acid, sodium hydroxide, ammonium hydroxide andthe like. In the presence of water and at higher temperaturescross-linking may occur without the addition of a condensation catalyst.In cross-linking it is believed the azide or diazo functional groupsreact with the polymers while the silyl groups condense, thus formingbonds between polymer chains.

The nitrogen containing silane compounds of this invention, as statedabove, have the general formula where X, T; R, Z, a, b, c, and d aredefined as above. Generally, R will be selected from the groupconsisting of the hydrocarbon, halo-substituted hydrocarbon,hydrocarbon-oxy-hydrocarbon, hydrocarbon-thio-hydrocarbon andhydrocarbon-sulfonylhydrocarbon divalent radicals. In preferredembodiments of this invention R will be a divalent organic radicalselected from the group consisting of alkylene radicals such as thestraight and branched C -C alkylene radicals which include, forinstance, the methylene, ethylene, trimethylene, tetramethylene,pentamelhylene, hexamethylene, octamethylene, decamethylene,dod'ecamethylene, octadecamethylene, etc. radicals; cycloalkyleneradicals such as the C -C cycloalkylene radicals which include, forinstance, the cyclohexylene,cycl0pentylene, cyclooctylene,cyclobutylene, etc. radicals; arylene radicals such as o.-, m-, andp-phenylene, naphthylene, biphenylene, etc. radicals; arylene-dialkyleneradicals; such as 0-, m-, and p-xylylene diethylene, o-, m-, andp-phenylene diethylene etc. radicals; alkylene-diarylene radicals suchas methylene bis (o-, mand p-phenylene), ethylene bis(0-, m-,and-p-phenylene), etc. radicals; cycloalkylene I dialkylene radicalssuch as, 1,2-, 1,3- and 1,4-cyclohexenedimethylene, 1,2- and1,3-cyclopentane dimethylene, etc. radicals; and thealkylene-oXy-alkylene radicals, aryleneoxy-arylene radicals,alkarylene-oxy-arylene radicals, alkarylene-oxy-alkarylene radicals,aralkylene-oXy-alkylene radicals, aralkylene-oxy-aralkylene radicals,etc. as well as the corresponding thio and sulfonyl radicals, specificexamples of which include ethylene-oxy-ethylene, propyleneoxy-butyle'ne,phenylene-oxy-phenylene, methylenephenyh ene oxy phenylenemethylene,phenylenemethylene-oxymethylenepheuylene, ethylene-thio-ethylene,phenylenethio-phenylene, phenylenemethylene-thio-methylenephenylene,*butylene-sulfonyl-butylene, etc. radicals. It will, of course, beobvious to those skilled in the art that R can contain otherfunctionalgroups, which are substantially inert to the reactions inwhich these compounds are used, such'as esters, sulfonate esters,amides, sulfonamides, urethanes, and the like. In general R can behydrogen, alkyl, cycloalkyl, aryl or -COOR radicals. The most preferredalkyl, cycloalkyl and aryl radicals are methyl, ethyl, propyl, butyl,isobutyl, cyclohexyl, cycloheptyl, phenyl, tolyl, etc. The radical R"can be alkyl, cycloalkyl, or aryl with the most preferred radicals beingmethyl, ethyl, propyl, butyl, isobutyl, cyclohexyl, cycloheptyl, phenyl,tolyl, etc. In general X can be hydroxy or any hydrolyzable radical.Typical hydrolyzable radicals are the halo radicals which include, forinstance, the fluoro, chloro, bromo and iodo radicals; the alkoxyradicals including the C -C straight and branched chain alkoxy radicalssuch as methoxy, ethoxy, propoxy, butoxy, isobutoxy, octadecyloxy, etc.;the aryloxy radicals such as phenoxy, etc.; the organo oxycarbonylradicals including the aliphatic oxycarbonyl radicals such as acetoxy,propionyloxy, stearoyloxy, etc.; the cycloaliphatic oxycarbonyl radicalssuch as cyclohexylcarbonyloxy, etc.; the aromatic oxycarbonyl radicalssuch as benzoyloxy, xylyloxy,'etc.; the azido radical; the amineradical; the substituted amine radicals such as ethylamine,diethylarnine, propylamine, etc.; and the amide radicals such asformamide, acetamide, trifiuoroacetamide, benzamide, etc. Generally Twill be a radical selected from the group consisting of alkyl,cycloalkyl, aryl, alkaryl, and aralkyl radicals such as methyl, ethyl,propyl, isopropyl,

butyl, hexyl, cyclohexyl, cycloheptyl, phenyl, tolyl, benzyl, xylvl,etc.

Typical nitrogen containing silane compounds of this invention are3-(trimethoxysilyl)propyl diazoacetate, Z-(methyldichlorosilyl)ethyldiazoacetate, p-(trimethoxysilyDbenzyl diazoacetate, 10-[(3-trirnethoxysilylpropyl carbamoyl] decyl diazoacetate,4-(trimethoxysilyl)butyl a-diazopropionate,3-(ethyldimethoxysilyl)propyl u-diazo-a-phenylacetate,3-(trichlorosilyl)propyl a-diazo-a-carbomethoxyacetate,2-(trimethoxysilyl) ethyl a-diazo-a-carbophenoxyacetate,4-(ethoxydichlorosilyl) cyclohexyl diazoacetate,3-(trimethoxysilyl)propyl azidoformate, 3-(methyldimethoxysilyl) propylazidoformate, 2-chloro-3- [3- (lrimethoxysilyl) propoxy] propylazidoformate, 3-triazidosilyl)propyl azidoformate,2-(trimethoxysilyl)ethyl azidoformate, 3(triacetoxysilyl) propylazidoformate, 2-[3-trimethoxysilyl)propoxy1ethyl azidoformate,3-(methy1diacetosilyl)propyl azidoformate, 2-(ethyldipropionyloxysilyl)ethyl azidoformate, p-(trimethoxysilyl)phenylazidoformate, 4-(diethoxychlorosilyl)butyl azidoformate, 4-(ethyldimethoxysilyl) cyclohexyl azidoformate,3-(phenyldichlorosilyl)propyl azidoformate, 4-(trisdimethylaminosilyl)butyl azidoformate, 5- (trimethoxysilyl)amylsulfonyl azide,4-(trimethoxysilyl)cyclohexylsulfonyl azide, 2-methyl-4-(trichlorosilyl)butylsulfonyl azide,3-chloro-6-(trimethoxysilyl)hexylsulfonyl azide,6-(trimethoxysilyl)hexylsulfonyl azide, 2-(trichlorosilyl)ethylsulfonylazide, 3-(dimethylaminodimethylsilyl) propylsulfonyl azide,2-(triethoxysilyl) ethylsulfonyl azide,3-(methyldimethoxysilyl)propylsulfonyl azide,3-(trimethoxysilyl)propylsulfonyl azide, 4- [diethoxy-(4-sulfonylazidobutyl) silyl] butylsulfonyl azide,p-(trimethoxysilyl)benzenesulfonyl azide,2-(trimethoxysilyl)ethyl-benzenesulfonyl azide,'N-3-(triethoxysilyl)propyl-N'-3-azidosulfonylpropylurea,N-3-(triethoxysilyl)propyl-N'-m-azidosulfonylphenylurea, etc.

HNO:

where T, X, R and 'R' are as defined above. The intermediate aminosilanecan be prepared, for example, by the addition of the desired silane toan unsaturated ester of glycine as follows:

0 l XSliH CHpCH-CHr-O-iil-CHr-NH:

where T and X are as defined above. If desired the unsaturated ester ofglycine can first be diazotized then reacted with the desired silane asfollows:

where T and X are as defined above. Still another method for thepreparation of the diazosilanes is the reaction of a hydroxydiazoacetate with a silaneisocyanate as follows:

where T, X and R are as defined above and x is greater than 1.

The azidosilane compounds, for example, can be prepared by reacting thecorresponding chloro-substituted compound with an alkali metal azide. Inthe preparation of an azidoformate the reaction can be shown as follows:

I I? ll x-s'i-n-oool NnN; X-SIi-R-OCN! where T, X, and R are as definedabove. The intermediate silane chloroformate can be prepared, forexample, by

the addition of the desired silane to an unsaturated chloroformate asfollows:

where T and X are as defined above, or an epoxysilane can be reactedwith phosgene as follows:

l X-S|i(CH2)aO-CHzCHCHz 0001,

I O1 i X--S|i(CHz)rO-CHz-(EHCHz-OC 01 where T and X are as definedabove. In the case of a sulfonyl azide the intermediate silanesulfonylchloride can be prepared for example by the addition of the desiredsilane to an unsaturated sulfonyl chloride as follows:

where T and X are as defined above, or an alkylsilane can bechlorosulfonated as follows:

where T and X are as defined above. It should be noted that a mixedreaction product may be obtained from chlorosulfonation, sincesubstitution is random along the alkyl chain and there will usually besome chlorination of the alkyl chain. Another method for the preparationof the azidosilanes is by reacting a compound containing the azido groupwith a compound containing the silane. In the case of sulfonyl azides anorganoaminosilane can be reacted with a compound containing both asulfonyl azide group and an isocyanate group as follows:

Where T and X are as defined above and x is greater than 1.

Many of the nitrogen containing silane compounds of this invention areliquids, that is liquid at 20-25 C. and at atmospheric pressure.However, some are solids. They are characterized in that the diazo orazido portion readily reacts with a wide variety of polymers to efifectilnkage of the polymer to the silane compound. They are furthercharacterized in that the silane portion of the molecule adheres tomaterials such as siliceous materials, metals, metal oxides and manypolymers.

The above described nitrogen containing silane compounds readilycondense to form dimers, trimers and even polymers when heated and/or inthe presence of water and acidic or basic condensation catalysts.Because of the ease with which they condense, it is apparent that manyof the silane compounds of this invention (with the exception of thosefreshly prepared under anhydrous conditions) exist in admixture with atleast a small amount of their condensation products. Therefore, it is tobe understood that the terms nitrogen containing silane compound andsilane compound, used in the specificatiou and claims of thisapplication, include not only the pure monomeric compounds but alsomixtures of the monomers with at least a small amount of thecondensation products of the monomers. It may be desirable in some casesto use a condensation product of a nitrogen containing silane compoundinstead of the monomer. If this is desired such condensation product canreadily be prepared by heating one of the above described silanecompounds in the presence of a small amount of water and a conventionalcondensation catalyst, i.e. acetic acid, HCl, HBr, NaOH, NH OH, or thelike. A typical dimer would hEWG the general formula where T, R, Z, cand d are as defined above. A typical condensation polymer would havethe general formula where X, T, R, Z, c and a are as defined above.

The following examples will illustrate the invention all parts andpercentages being by weight unless otherwise indicated.

EXAMPLE 1 This example illustrates N-3-(triethoxysilyl)propyl-N-m-azidosulfonylphenylurea, and a process for its preparation.

To a solution of 15 parts of m-azidosulfonylphenyl isocyanate in 150parts of benzene at room temperature was added dropwise 14.8 parts of3-aminopropyltrietl1- oxysilane with stirring. As the triethoxysilanewas added, a white needlelike solid began to form. The addition of 25parts of methylene chloride resulted in a clear solu- 8 tion. Afterstirring overnight the solvent was evaporated leaving a yellow solidhaving a melting point of -95 C.

An infra-red spectrum of this product showed a strong azide band at 2130cm.- and a strong carbonyl band at 1700 cm.- A sample of the productdecomposed in diphenyl ether at 153 C. evolving 92% of the theoreticalamount of gas.

A typical elemental analysis of this product was: Analyzed (percent): N,14.6; S, 7.3; Si, 6.2. Calculated (percent): N, 15.7; S, 7.2; Si, 6.4. Asample of the product recrystallized from a mixed benzene-hexane solventwas white and melted at 95-97 C.

EXAMPLE 2 This example illustrates 3- (methyldimethoxysilyl) propylazidoformate and a process for its preparation.

To a solution of methyldichlorosilane parts) and allyl chloroformate (60parts) was added chloroplatinic acid (0.0052 part) dissolved inisopropanol (0.1 part). The mixture thus formed was stirred at 2025 C.under nitrogen for about 144 hours. Volatiles were removed by aspiratorvacuum from the reaction mixtureLSubscquently the reaction mixture wasvacuum distilled. A middle cut (35 parts) boiling at 656 8 C. at apressure of 0.4 millimeter of mercury was collected as the desiredintermediate product. It consisted essentially of3-(methyldichlorosilyl)propy1 chloroformate.

A portion (21 parts) of this intermediate product was added to a slurryof sodium azide (46.2 parts) in anhydrous methanol parts). The resultingmixture was stirred rapidly in a nitrogen atmosphere for about 144 hoursat 20-25 C. The reaction mixture was placed under aspirator vacuum toremove solvent. The residue, a pasty solid, was extracted with methylenechloride. The colorless extract solution was subjected to vacuum toremove substantially all of the solvent. The residue was a colorless oil(37.6 parts) consisting essentially of 3-(methyldimethoxysilyl)propylazidoformate.

A typical elemental analysis of this product was: Analyzed (percent):-N, 16.2; Si, 12.1; C1, 0.1. Calculated (percent): N, 18.0; Si, 12.0;Cl, 0.

EXAMPLE 3 This example illustrates 3- (trimethoxysilyl)propylazidoformate and a process for its preparation.

To a solution of trichlorosilane (67.5 parts) and allyl chloroformate(30 parts) was added a solution of chloroplatinic acid (0.0052 part) inisopropanol (0.1 part). The resulting mixture was stirred for 45 hoursat 20-25 C. It was then subjected to vacuum distillation, the fractiondistilling at 48-50 C. at a pressure of 0.35 millimeter of mercury beingcollected as the desired intermediate product (28 parts). This productconsisted essentially of 3-'(trichlorosilyl)propyl chloroformate.

This intermediate product (23 parts) was added dropwise to a slurry ofsodium azide (39 parts) in anhydrous methanol (100 parts) whilemaintaining the reaction mixture thus formed at 20-25 C. After stirringat this temperature in a nitrogen atmosphere for 20 hours, the reactionmixture was sparged with nitrogen and then stripped by aspirator vacuumof solvent. The white pasty residue was extracted with methylenechloride, the solidsliquid separation being achieved by centrifugationand decantation. The remaining solids were extracted two more times withfresh methylene chloride with the resulting methylene chloride extractsbeing combined with the first methylene chloride extract. The totalmethylene chloride extract was subjected to aspirator vacuum and thenhigh vacuum (0.5 millimeter of mercury} at 20 25" C. The residue was acolorless liquid (19.9 parts) consisting essentially of 3(trimethoxysilyl(propyl azidoformate.

An infra-red spectrum of this product showed a strong azide doublet at2140 cn'nand 2180 cmr and a strong carbonyl band at 1740 cmr A typicalelemental analysis of this product was: Analyzed (percent): N, 16.6; Si,10.1; Cl, 0.81. Calculated (percent): N, 16.8; Si, 11.2; C1, 0.

EXAMPLE 4 This example illustrates 2 chloro3-[3-(trimethoxysilyl).propoxy]propy1 azidoformate, and a process forits preparation.

Liquid phosgene (20 parts) was added to a flask containing pyridine (1part) at 60 C. The resulting yellow slurry was warmed to 15 C. and3-glycidoxypropyl trlmethoxysilane (23.6 parts) added dropwise over a 30minute period. The yellow reaction mixture was stirred for 1.5 hours at15 to 10 C., and then placed in a wet ice bath (-|-3 C.) under a veryslow nitrogen sparge. The wet ice bath was allowed to warm to 2025 C.over a period of 16 hours. The resulting reaction mixture (a tan coloredslurry) was sparged with nitrogen and then subjected to high vacuum at2025 C. The residue was a light amber oil containing a small quantity ofwhite solids. The solids were separated from the oil by centrifugation,to give the desired intermediate product (29 parts). This intermediateproduct consisted essentially of 2- chloro 3 [3trimethoxysilyl)propoxyJpropyl chloroformate.

A portion (13.4 parts) of the intermediate product was added dropwise toa slurry of sodium azide (7.8 parts) in anhydrous methanol (100 parts)maintained at 20- 25 C. The resulting reaction mixture was stirred for20 hours at 2()25 C. under nitrogen. The white slurry thus obtained wasstripped under aspirator vacuum and then extracted with methylenechloride. The extract was subjected to high vacuum at 2025 C. to removesubstantially all of the solvent. The resulting product was an oil (12.5parts), consisting essentially of 2-chloro-3-[3-(trimethoxysilyl)propoxy]propyl azidoformate.

The infra-red spectrum of this product showed a strong azide doublet at2140 cm." and 2185 cm.* as well as a carbonyl band at 1740 cm.-

A typical elemental analysis of the product was: Analyzed (percent): N,11.6; Si, 7.7; Cl, 10.8. Calculated (percent): N, 12.3; Si, 8.2; Cl,10.4.

EXAMPLE 5 This example illustrates 3-(triazidosilyl)propyl azideformateand a process for its preparation.

Liquid sulfur dioxide (40 parts) was collected in a Dry Ice-acetonebath, warmed to 20 C., and sodium azide (3.25 parts) admixed with it.While stirring the resulting white slurry at C., a portion (2.56 parts)of 3-(trichlorosilyl)propyl chloroformate was added. The reactionmixture thus formed was stirred at 10 C. for 3 hours and then allowed toslowly warm to 20-25" C. while passing a stream of nitrogen through thereaction mixture and evaporating excess sulfur dioxide. Methylenechloride (60 parts) was added to the remaining white solid material, andthe mixture was then centrifuged to remove insoluble material. Thesolution was then stripped of methylene chloride by sparging with astream of nitrogen until a constant weight was reached. The materialthat remained was a colorless oil (2.49 parts) consisting essentially of3-(triazidosilyl)propyl azidoformate.

The infra-red spectrum of the oily product displayed a strong azide bandat 2160 cm? as well as a carbonyl band for the azidoformate at 1730 cmr'The azide content of the oil analyzed 59.2%. The calculated azidecontent for 3 (triazidosilyl)propyl azidoformate is 59.5%.

EXAMPLE 6 This example illustrates mixed isomers of chlorinated(trimethoxysilyl)amylsulfonyl azide and a process for their preparation.

Amyltrichlorosilane (41 parts) in carbon tetrachloride (250 parts)containing pyridine (0.5 part), was exposed to ultraviolet light whilesulfuryl chloride (48.5 parts) was added dropwise over a period of 1hour. The temperature was maintained at 2530 C. during the addition. Themixture thus formed was stirred for 7 hours at 25- 30 C. with continuedexposure to ultraviolet light. A slightly cloudy solution resulted.Volatiles were removed from the solution by heating to C. at atmosphericpressure, and then subjecting it to high vacuum at 2025 C. The productthat remained was an amber oil (54 parts) consisting essentially ofmixed isomers of chlorinated (trimethoxysilyl)amylsulfonyl chloride.

A portion (45 parts) of the intermediate product was added dropwise to aslurry of sodium azide (57 parts) in anhydrous methanol (300 parts)maintained at 20-25 C. The resulting reaction mixture was stirred at2025 C. for 20 hours, and then the methanol removed at this temperatureby aspirator vacuum. The residue was a reddish tan pasty solid material.It was diluted with methylene chloride and the solids removed bycentrifugation. The yellow solution remaining was subjected, at 20-25C., to a vacuum of 0.5 millimeter of mercury to remove the methylenechloride. The residue was a yellow oil (39.4 parts) consistingessentially of mixed isomers of chlorinated(trimethoxysilyl)amylsulfonyl azide.

The infra-red spectrum of the product in methylene chloride shows anazide band at 2145 CDT-1, and sulfonyl bands at 1370cm. and 1190 cm.

A typical isomer contains one chloride on the amyl chain and onesulfonyl azide group also on the amyl chain.

EXAMPLE 7 This example illustrates mixed isomers of(trimethoxysilyl)hexylsulfonyl azide and a process for theirpreparation.

A solution of n-hexyltrichlorosilane (102 parts) in methylene chloride(1200 parts) was cooled to 3 C. Sulfur dioxide gas was bubbled throughthe solution at a rate of about 9 parts per hour for about 10 minutes.Chlorine gas (25 parts) was then introduced in conjunction with thesulfur dioxide gas over a 5 hour period 7 into the reaction mixture at 5C. while exposing to ultraviolet light. The solvent was removed byaspirator vacuum from the chlorosulfonated reaction mixture. Theresulting pale yellow solution was subjected to vacuum distillation upto 65 C. at 0.5 millimeter of mercury to remove unreactedn-hexyltrichlorosilane. The oily residue (345 parts) was an intermediateproduct consisting essentially of mixed isomers of(trimethoxysilyl)hexylsulfonyl chloride.

A quantity (159 parts) of the intermediate product was added dropwise toa slurry of sodium azide parts) in anhydrous methanol (850 parts) whilemaintaining the temperature at 2025 C. After stirring the reactionmixture at this temperature for about 20 hours, the pink slurry wassparged with nitrogen and then stripped by aspirator vacuum of solvent.Benzene (450' parts) was admixed with the reaction mixture and the thusdiluted mixture filtered. The filtrate was washed with fresh benzene(250 parts) and the wash liquid and filtrate combined to give a clearcolorless solution (800 parts). This solution was stripped of benzene at35 C. at 0.5 millimeter of mercury. The residue was a colorless oil (142parts) consisting essentially of mixed isomers of(trimethoxysilyl)hexylsulfonyl azide.

An infra-red spectrum of the product showed an azide band at 2130 cm.-1as well as sulfonyl peaks at 1365 cm." and 1160 CHI-1.

A typical elemental analysis of the product was: Analyzed (percent): N,12.8; S, 9.7; Total C1, 2.6. Calculated (percent): N, 13.5; S, 10.3;Total Cl, 0. The small amount of chlorine found in the analysis of theproduct indicates that the hexyl chain was partially chlorinated.

1 1 EXAMPLE 8 his example illustrates mixed isomers of(trimethoxysilyl)cyclohexylsulfonyl azide and a process for theirpreparation.

A solution of cyclohexyltrichlorosilane (100 parts) in methylenechloride (1200 parts) was cooled to 3 C. and sulfur dioxide gas bubbledinto the solution at a rate of 11.8 g. per hour for a period of about 15minutes. While exposing the reaction mixture to ultra-violet light,chlorine gas (32.5 parts) was introduced into the reaction mixture inconjunction with the sulfur dioxide gas over a period of about 5 hours.Upon completion of the introduction of chlorine gas, exposure of thereaction mixture to ultra-violet light was continued for an additional30 minutes. The solvent was removed from the clear solution underaspirator vacuum and then unreacted material was removed by distillationat 40 C. and pressure of 0.5 millimeter of mercury. The yellow oilyresidue (66 parts) consisted essentially of mixed isomers of(trichlorosilyl)cyclohexylsulfonyl chloride.

This intermediate product (60 parts) was added dropwise to a slurry ofsodium azide (74 parts) in anhydrous methanol (500 parts). The resultingmixture was stirred at 20-25 C. in a nitrogen atmosphere for 20 hours.After removal of methanol by aspirator vacuum, benzene (300 parts) wasadmixed with the reaction mixture and the resulting slurry centrifugedto remove insolubles. The liquid that remained was a clear pale yellowsolution. By subjecting the solution to a vacuum of 0.5 millimeter ofmercury at a temperature of about 30 C., the benzene was stripped fromthe solution, giving a yellow oily product (45.5 parts) consistingessentially of mixed isomers of (trimethoxysilylcyclohexylsulfonylazide.

An infra-red spectrum of the product showed a strong azide peak at 2145cm? and sulfonyl bands at 1370 cm.- and 1160 amt-1.

A typical elemental analysis of the product was: Analyzed (percent): N,11.6; S, 8.6; Si, 8.9; Total CI, 3.1. Calculated (percent): N, 13.6; S,10.3; Si, 9.05; Total Cl, 0. The small amount of chlorine found in theanalysis of the product indicates that the cyclohexyl ring was partiallychlorinated.

EXAMPLE 9 This example illustrates 3(trimethoxysilyl)propyl diazoacetateand a process for its preparation.

A mixture of glycinyl chloride hydrochloride (13 parts) and allylalcohol (11.6 parts) was heated under an atmosphere of nitrogen for 2hours at 90 C. The resulting mixture was extracted thoroughly with etherto remove excess allyl alcohol and the remaining insoluble materialdissolved in water (50 parts). Ether (180 parts) was added to theaqueous solution and sodium nitrite (6.9 parts) dissolved in the aqueouslayer while maintaining the temperature at C. Then 10% sulfuric acid wasadded dropwise until the ether layer became bright yellow. The etherlayer was separated from the aqueous layer and dried over a mixture ofanhydrous sodium sulfate and anhydrous sodium carbonate. The dryingagents were filtered off and the ether removed under vacuum. The yellowoily residue consisted essentially of allyl diazoacetate.

A portion of the intermediate product parts), along withtrimethoxysilane (12.2 parts) and a catalytic amount of azobis-isobutyronitrile were dissolved in benzene (175 parts) and heatedfor 16 hours at 50 C. The benzene and excess silane were then removedunder vacuum. The yellow oily residue consisted of3(trimethoxysilyl)propyl diazoacetate in substantial yield.

EXAMPLE This example illustrates mixed isomers of 3- and4-(trimethoxysilyl)cyclohexy1 diazoacetate and a process for theirpreparation.

A mixture of glycinyl chloride hydrochloride (9' parts) and3-cyclohexene-1-o1 (14.7 parts) was heated under an atmosphere ofnitrogen for 2 hours at C. The resulting mixture was extractedthoroughly with ether and the remaining insoluble material dissolved inwater (40 parts). Ether parts) was added to the aqueous solution andsodium nitrite (4.75 parts) dissolved in the aqueous layer while coolingthe whole to a. temperature of 0 C. Then 10% sulfuric acid was addeddropwise until the ether layer became bright yellow. The ether layer wasseparated and dried as described in Example 9. The drying agents werefiltered ofi and the ether removed under vacuum. The remaining yellowoil consisted essentially of 3-cyclohexene-l-diazoacetate.

A portion of the intermediate product (4.2 parts), along withtrimethoxysilane (12.2 parts) and a catalytic amount of azobis-isobutyronitrile were dissolved in benzene parts) and heated for 14hours at 50 C. The benzene and excess silane were then removed undervacuum. The yellow oily residue consisted essentially of 3- and4-(trimethoxysilyl)cyclohexyl diazoacetate in substantial yield.

EXAMPLE 1 1 This example illustrates p-[3-(trimethoxysilyDpropyH phenyldiazoacetate and a process for its preparation.

Glycinyl chloride hydrochloride was reacted with3-(phydroxyphenyl)-1-propane and then diazotized using the processdescribed in Examples 9' and 10.

The resulting intermediate (9.1 parts), along with trimethoxysilane 12.2parts) and a catalytic amount of azo bisisobutyronitrile were dissolvedin benzene (130 parts) and heated for 15 hours at 50 C. The benzene andexcess silane were removed under vacuum. The yellow oily residueconsisted essentially of p-[3-(trimethoxysilyl) propyl]phenyldiazoacetate in good yield.

EXAMPLE 12 This example illustrates 10-[(3-trimethoxysilylpropyl)carbamoyHdecyl diazoacetate and a process for its preparation.

To melted 1,10-decanediol (35 parts) at 125 C. was added glycinylchloride hydrochloride (11.24 parts) portionwise under an atmosphere ofnitrogen over a one hour period with stirring. The resulting mixture washeated under nitrogen for 2 hours at 120 C. Water (500 parts) was addedand the mixture stirred 4 hours. It was then extracted four times withportions of chloroform (300 parts). The aqueous layer was filtered andevaporated to dryness to give an orange gummy solid. The solid wasextracted with ether and dissolved in water (100 parts). Ether (210parts) was added to the resulting yellow aqueous solution and themixture cooled to 0 C. Sodium nitrite (50 parts) was dissolved in theaqueous layer and 10% sulfuric acid added dropwise. With the addition ofacid the ether layer became yellow and was periodically drawn off andreplaced with fresh ether. The combined ethereal extracts (850 parts)were dried as described in Example 9. The drying agents were filteredolf and the ether removed under vacuum. The remaining yellow oil (6.4parts) consisted essentially of IO-hydroxydecyl diazoacetate.

A portion of the intermediate product (5.63 parts), along with3-(trimethoxysilyl)propyl isocyanate (4.76 parts) and a few drops ofdibutyl tin dichloride were added to benzene (45 parts) and stirred for5 days under an atmosphere of nitrogen at room temperature. The benzenewas then removed under vacuum leaving a yellow oily product. Theresulting product was 10-[(3-trimethoxysilylpropyl)carbamoyl]decyldiazoacetate of approximately 81% purity as determined by nitrogenevolution.

EXAMPLE 13 This example illustrates the bonding of a polymer to a steelpanel by first treating the polymer with an azidosilane compound.

A colloidal suspension of approximately 20-22% total solids crystallinepolypropylene particles, having an average particle size within therange of 0.02-0.5 micron, in a mixed aliphatic hydrocarbon solvent,having a boiling point of 165 C. to 200 C., was divided into fourportions. To each portion of the colloidal suspension was added adifferent amount of 2-chloro-3-[3-(trimethoxysilyl)propoxy]propylazidoformate in a methylene chloride solution. Each suspension wasmechanically mixed and then used to dip-coat an iron phosphate treatedsteel panel. Each coated panel was baked at a temperature of 400 F. foreight minutes and then allowed to cool. The coating on each panel wastested for adherence by scoring with a razor blade and then drawing theedge of a metal coin firmly across the thus scored surface. The adhesionof the coating to the surface was rated as follows:

The results of the test are tabulated below:

Percent of azidosilane in suspension 1 Adhesion Poor.

0. 1 Good. 0. 5 Excellent. 1. Do.

1 Percent by weight based on the weight of polypropylene.

2 None (control).

EXAMPLE 14 This example illustrates the bonding of a polymer to metalpanels by first treating the panels with an azidosilane compound.

Metal panels 1 x 4 inches and inch thick were cleaned and then degreasedin trichloroethylene vapor. Each panel, except the untreated controls,was treated by dipping in a solution of 0.02 g./ml. of2-chloro-3-[3-(trimethoxysilyl)propoxy]propyl azidoformate in methylenechloride solution for approximately 5 seconds and immediately dried witha cold air gun. Samples of each polymer were cut into 0.050 inch thick 1x /2 inch plaques, cleaned and placed between two metal panels so thatthe panels overlapped approximately /2 inch. Each assembly was molded ina hydraulic press for 5 minutes at an elevated temperature and apressure of 400 p.s.i. and then cooled in the press to room temperature.In each case the assembly was placed in a jig during the molding tomaintain a 0.025 inch glue line. Each sample was then tested for lapshear strength. The metal panels and polymers used, the temperature ofthe pressure molding and the results of the lap shear strength tests aretabulated below.

14 EXAMPLE 15 This example shows the bonding of polypropylene to metalpanels by first treating the panels with an azidosilane compound.

Metal panels 1 x 4 inches and inch thick were cleaned and then treatedwith a methylene chloride solution of an azidosilane compound exactly adescribed in Example 14. The panels were assembled for lap shearstrength tests by placing plaques of polypropylene between two panelsalso as described in Example 14 and molding at a temperature of 230 C.for 5 minutes. The time was used as follows: 3 minutes at contactpressure, 1 minute up to a pressure of 200 p.s.i. and 1 minute atpressure. Each molded sample was then tested for lap shear strength. Themetal panels used, the azidosilane compound used and its concentrationin the methylene chloride solution and the results of the tests aretabulated below.

Azidosilane Sulionyl azide 1 D0 0 1, 900 rolled stee 2, 000

E Mixed isomers of (trimethoxysllyDhexylsulfonyl azide described in xampMixed isomers of chlorinated (trimethoxysilyl)amylsultonyl azidedescribed in Example 6.

d Cold EXAMPLE 16 This example shows the bonding of a polypropylenesuspension to metal panels by first treating the panels with anazidosilane compound.

The procedure used in this example is similar to that described inExample 14 except the panels were treated by dipping in a 5% aqueousmethanol solution of 0.02 g./rnl. of 3-(trimethoxysilyl)propylazidoformate. Each panel was coated on one side, using a 10 mil drawdownknife, with the colloidal suspension of crystalline polypropyleneparticles described in Example 13. The coatings were fused at -200 C.for 7 minutes. The resulting films were approximately 0.7-1.0 mil inthickness. Plaques (40 mils thick) of the crystalline polypropylene filmdescribed in footnote 1 of Example 14 were placed between the coatedpanels as described in Example 14 and molded as described in Example 15.The molded X Crystalline polypropylene having a specific gravity of0.904 g./cc. and a melt index (I: at 230 C.) of 4.

2 High density polyethylene having a specific gravity of 0.952 g./cc.and a melt index (I2 at 190 0.) of 0.6.

I High density polyethylene having a specific gravity of 0.945 g./cc.

samples were then tested for lap shear strength and the resultstabulated below:

Lap shear bond Metal: strength, p.s.i. Cold rolled steel 2000 Aluminum2300 EXAMPLE 17 This example shows the bonding of a polypropylenesuspension to metal panels and lap shear bond strength tests where thepolypropylene is first mixed with an azidosilane compound.

Samples of the colloidal suspension of crystalline polypropyleneparticles described in Example 13 were mixed with various amounts ofazidosilane in methylene chloride solution.

Metal panels were coated with the polymer suspension and fused asdescribed in Example 16. Then the coated panels were assembled andmolded also as described in Example 16. The molded samples were testedfor lap shear strength. The metal panels used, the azidosilane compoundused and the amount and the results of the tests are tabulated below:

Lap shear bond Amount, strength, psi.

Azldosilane percent 1 Metal panel 3-(trimethoxysllyl) propylazidoiormate.

1 Percentage by weight based on the weight at polypropylene. I Asdescribed in footnote 1 of Example 15.

EXAMPLE 18 This example shows the bonding of polypropylene to glasscloth which has first been treated with an azidosilane compound.

Twelve (12) ply laminates of glass cloth and polypropylene film wereprepared using 181 style electrical glass woven cloth, heat cleaned andhaving a weight of 8.9 ounces per square yard and 5 mil film ofcrystalline polypropylene. Sheets of the glass cloth were first immersedin a 0.09 g./ml. solution of 2-chloro-3 [3-(trimethoxysilyl)propoxy1propyl azi-dot'ormate in methyl chloride. The thus treated clothwas dried and then laid up to form the laminate by alternating plies ofthe treated glass cloth and sheets of the polypropylene film. Theresulting assembly was compression molded at a temperature of 220 C. for7 minutes at contact pressure, 3 minutes at a pressure of 440 p.s.i. andthen cooled to 23 C. under 440 p.s.i. pressure to form a A3 inch thicklaminate. A control laminate was prepared exactly as described aboveexcept the treatment with the azidosilane was omitted. Test specimens 1inch by 3 inches were cut from the laminates and tested for flexuralstrength and flexural modulus according to ASTM D-790 on a 2 inch spanat 0.05 inch/minute crosshead speed. The results are tabulated below:

EXAMPLES 19-30 These examples show the bonding of various polymers toglass cloth which have first been treated with an amidesilane compound.

Strips of the glass cloth described in Example 18 were immersed in a0.5% by weight solution of 2-chloro-3[3-(trimethoxysilyl)propoxyjlpropyl azidoformate in methylene chloride,drained and hung to dry. The resulting treated glass cloth was used toprepare '12 ply laminates with 12 different polymers as follows:

(19) Strips of the treated glass cloth were immersed in a 12.5% byweight solution of polycarbonate resin in methylene chloride. The stripswere hung up to dry and then heated in an oven at a temperature of 70 C.to remove the last traces of solvent. The resulting sheets were cut intosquares measuring 5% x 5% inches. Twelve plies of the polymerimpregnated cloth were assembled for molding.

(20) A twelve ply assembly was prepared exactly as described in 19except the strips were immersed in a 33% by weight solution ofacrylonitrile-butadiene styrene molding powder in methylene chloride.

(21) A strip of the treated glass cloth was cut into squares measuring5% x 5% inches. A laminate was assembled by alternating 12 plies of theglass cloth squares with 13 plies of crystalline polypropylene film 5mils in thickness.

(22) A laminate was assembled exactly as described in 21 except thepolymer was 6 mil polyethylene.

(23) A laminate was assembled exactly as described in 21 except thepolymer was 5 mil pressed sheets of polystyrene.

(24) A laminate was assembled exactly as described in 21 except thepolymer was 5 mil pressed sheets of polyoxymethylene.

(25) A laminate was assembled exactly as described in 21 except thepolymer was 5 mil poly(vinyl chloride) film.

(26) A laminate was assembled exactly as described in 21 except thepolymer was 5 mil nylon film.

(27) A laminate was assembled exactly as described in 21 except thepolymer was 6 mil poly(ethylene terephthalate) film.

(28) A laminate was assembled exactly as described in 21 except thepolymer was 6 mil poly(ethylene terephthalate-hexahydroterephthalate)film.

(29) A laminate was assembled using 12 squares of the treated glasscloth. Each square measured 5% x 5% inches and was coated with a hotepoxy resin. The resin was prepared by heating 15 parts of the epoxyresin to 50 C. and adding 1.87 parts of m-phenylenediamine. The laminatewas assembled on a heated 12 x 12 inch steel plate fitted with apoly(ethylene terephthalate) release sheet. An excess of resin wasmaintained on the laminate at all times and as each square of cloth wasadded, a spatula was used to work the trapped air through the cloth.One-eighth inch spacer bars were placed on three sides of the laminateand a release sheet placed on top. A second steel plate was placed onthe laminate and the entire assembly secured with C-clamps.

(30) A laminate was assembled exactly as described in 29 except thepolymer was a styrene-modified polyester resin mixed with 1 part perhundred methyl ethyl ketone peroxide and heated to 60 C.

All thermoplastic laminates were prepared by compression molding in apicture-frame mold having inside dimensions of 6 x 6 x inches. Moldingconditions are given in Table I.

The thermosetting plastic laminates were gelled and cured while clampedbetween steel plates. The conditions are given in Table II.

TABLE I Preheat Molding Cooling, Time, Temp, Press., Time, Temp., Press.press. Polymer min. C. p s.i. min. C. p.s.i. p.s.i.

Example N0.:

19 Polycarbonate 1 4 250 Contact...-. 5 250 500 500Acrylonitrile-butadlene-styrene 7 240 -.do 5 240 350 350 Polypropylene 75 220 400 400 Polyethylene 4 6 4 177 400 400 Polystyrene 6 4 204 340 340Polyoxymethylene 4 3 220 340 340 Poly (vinyl chloride) 15 3 193 440 440Nylon 8 10 2 280 500 600 Poly (ethylene terephthalate) I 7 285 500 11500 Poly (ethylene terephthalate- 4 3 235 400 11 400hexahydroterephthalate) 1 Based on 4,4-dihydroxydiphenylpropane andhaving a melt index (ASTM D-1238) 015 g.l10 min.

i 19% acrylonitrile, butadiene having a melt index (ASTM D-1238) of 16g./10 mi 8 Crystalline, having a specific gravity of 0.904 g./cc. and amelt index 014 g./l0 min.

11. (I at 230 0.).

High density, having a specific gravity of 0.952 g./cc. and a melt indexoi 0.6g./10 min. (I at 190 0.).

5 Atactic polystyrene having a specific gravity of 1.04 g./cc.

" Having a specific gravity of 1.42 g./cc.

Z gig-1% having a number average molecular weight of 140,000.

hexamethylene adipamide) having a number average molecular weight of110,000.

' Having an intrinsic viscosity of 0.61 and an amorphous specificgravity 0! 1.34 g./cc.

Havings a specific viscosity of 0.85 at C. in a 60/40 solution of g./cc.after annealing.

2 hours at 135 C. under pressure.

phenol and tetrachloroethane and a specific gravity ol' 1.335

l1 Annealed for 7 TABLE H EXAMPLES 31 AND 32 t t' Example No Polymer Gelcondi ions Cure condi ions 25 These examples Show the bondmg of P yp pye to 29 Epoxy resin 1 1 hr. at 120 C. 3 hrs. at 160 C. 1 Polyester resin3 at 6t0;5g ,C 1 hr. at 180 C. have first been treated wlth IS. 8

Strips of the glass cloth described in Example 18 were 1 s e a ufiaififitigli i igf ether Bisphenol A having an epoxma immersed insolution of an azldosilane in methylene chlostyrene'modifiedbisphenol-type Polyester 30 ride, drained and hung to dry. The resultingtreated glass Control samples were prepared exactly as described clothwas used to prepare 12 ply laminates with crystalline above except thatthe glass cloth was not first treated polypropylene film, 5 mils inthickness exactly as dewith the azidosilane compound. Samples of thetreated scribed in Example 18. Control samples were prepared and controllaminates were tested for flexural strength and m the Same manner exceptthe glass cloth was not modulus according to ASTM D-790 using a 2 inchspan, first treated with an azldosllane compound. Samples weresingle-point loading, and a crosshead speed of 0.2 inch/ cut from thetreated and control laminates and tested for minute. Each sample was cutto a size of 1 x 3 x A; inch. flexural strength and modulus according toASTM D- TABLE III Dry flexural properties Boiled in water propertiesTreatment of Strength, Modulus, Hours Strength, Modulus Polymer glasscloth p.s.i. p.s.i.X10 boiled p.s.i. p.s.i.X10

Exam le N0.:

19?. Polycarbonate Treated 52, 200 2.7 72 24,000 2.2

Control. so, 200 2. 4 72 21, 300 2. 0 20Acrylonitrile-butadiene-styrene-.-.Swamp... fig, 8 2g, on re 21Polypropylene -.{Treated 381100 2. 2 72 31,000 2.1 Control-. 12, 500 1.8 72 8, 1. 4 22 Polyethylene {Treate 22,800 1.5 72 20, 400 1.8 Control13, 200 1. 2 72 200 1. 3 23 Polystyrene {Treate 49,100 2.4 72 34,600 1.8Control. 5,000 3.0 72 18,200 2.0 24 Polyoxymethylene 1 res te? gngg 0111'0 25 Poly(vinyl chloride) 'I re:2te li ggggg 9 m on re 26 Nylon-{Treated 56,600 2.8 72 30,500 1.8 Control 43, 000 2. 6 72 500 1. 4 27Poly(ethylene terephthalate) 31152212831 g, g, on to 28 Pg y y g g g l aa e aa e i 23.188 g 38g otere a e 011 ro 29 Epgxy resin .JTreated-.- 67300 2. 7 72 5 1, 200 2. 8 lControl-.- 47, 300 2. 2 72 36, 100 2. a 30Polyester resin -.{Treated 55, 700 3. 5 72 35,400 3. 0 Control 51, 8002. e 72 25, 600 2. e

Tests were also conducted on most of the samples after boiling in water.The results of the tests are set forth in Table III.

790. Tests were also conducted On the samples after boiling in water.The results of the tests are set forth in Table IV.

TABLE IV Dry flexural 72 hour boll flexural Azldosilane propertiesproperties conc. (wt.

percent) Strength, Modulus, Strength, Modulus, Example No. Azidosllane H01 p.s.i. p.s.i. (10 p.s.i. p.s.i.X10

Control--.-. 0 12, 500 1. 8 8, 100 1. 4 Sullonyl azide 1 0. 36, 100 2. 521, 100 1. 8 ii 0. 250 39, 400 2. 4 24, 300 2. 2 0. 500 45, 100 2. 3 0002. 4 1.00 36, 400 2.0 26, 300 2. 4 0 125 35, 900 2. 5 2. 1 32 propylazidoiormate.

- o 0.250 36, 200 2.5 25,600 2.2 do 0. 500 32, 300 2. 6 21, 600 2. 3

1 & described in footnote 2 0t Example 15.

19 EXAMPLE 33 A laminate was prepared exactly as described in Example 32except the glass cloth was immersed in an aqueous solution of theazidosilane instead of a methylene chloride solution. The aqueoussolution was prepared as follows: A methylene chloride solutioncontaining 0.0024 g./ml. of 3-(trimethoxysilyl)propyl azidoformate wasdiluted with equal parts of acetone. The resulting solution was heatedto distill off the methylene chloride. A portion of the resultingacetone solution amounting to 33 ml. was diluted to a total volume of200 ml. with distilled water. Then the pH of the solution was adjustedto 4 with glacial acetic acid.

A sample of the laminate and a control were tested for flexural strengthand modulus as described in Examples 31 and 32. The results of the testsare tabulated below.

Dry flexural 72 hour boil properties flexure' l {properties Strength,Modulus, Strength, Modulus, p.s.i. p.s.i.X10 p.s.i. p.s.LXIOfl Control12,500 1. 8 8, 100 1. 4 Treated 21, 900 2. 0 18, 200 1. 9

Strips of the glass cloth described in Example 6 were immersed in anaqueous dispersion prepared as follows: To 200 parts of water containinga small amount of alkylphenoxy poly(ethyleneoxy ethanol) nonionicsurfactant was added with vigorous agitation 10 parts (based on thesolids) of an aqueous dispersion of poly(vinyl acetate) having aBrookfield viscosity of 10 poises at C. and a pH of 5.0. Then 10 partsof crystalline polypropylene particles, having an average particle sizewithin the range of 0.02-05 micron, and 1 part of the mixed isomers of(trimethoxysilyl) hexylsulfonyl azide described in Example 7 were addedwith continued agitation. After immersion, the strips were hung up todry and then cut into 5% inch squares for lamination. Twelve squares ofthe sized sheet were alternately laid up with 5 mil sheets ofcrystalline polypropylene and compression molded at a temperature of 220C. for 7 minutes at contact pressure, 3 minutes at a pressure of 440p.s.i. and then cooled to 23 C. under 440 p.s.i. pressure. Testspecimens were cut from the laminates and tested for flexural strengthand modulus according to ASTM D-790. Tests were also conducted on thesamples after boiling in water for 72 hours. The results of the testsare tabulated below.

Dry fiexural 72 hour boil flexural Grams of properties propertiesazidosilane Percent in sizing Strength, Modulus, Strength, Modulus,Strength dispersion p.s.i. p.s.i.}(lO p.s.i. p.s.LXlO retention EXAMPLES34 AND 35 These examples show the bonding of polypropylene to samples ofglass cloth which have first been treated with an azidosilane compound.

Strips of the glass cloth described in Example 18 were immersed inbenzene or methylene chloride solutions of an azidosilane, drained andhung to dry. The resulting treated glass cloth was used to prepare 12ply laminates with crystalline polypropylene film, 5 mils in thicknessexactly as described in Example 18. Control samples were prepared in thesame manner except the glass cloth was not first treated with anazidosilane compound. Samples were cut from the treated and controllaminates and tested for flexural strength and modulus according to ASTMD-790. Tests were also conducted on the samples after boiling in waterfor 72 hours. The results of the tests are set forth in Table V.

EXAMPLES 37-39 These examples show the bonding of various polymers toglass cloth by first treating the polymers with an azidosilane,

In each example, 15 parts by weight of polymer was added toapproximately 1300 parts by weight of dry tetrachloroethylene. 'Amethylene chloride solution of 0.67 part by weight of3-(trimethoxysilyl)propyl azidoformate was then added and the wholeheated to 120 C. with stirring. After 90 minutes the solution was cooledto 90 C. and 1 part by weight of water added to promote silanehydrolysis. Strips of the glass cloth described in Example 18 wereimmersed for 10 minutes in the hot solution, hung in a hood for 15minutes and then dried for 16 hours at 80 C. in a vacuum oven. The driedstrips were cut into 5% inch squares. The thus coated cloth squares werelaid up to form the laminates by alternating plies of the TAB LE V Dry72 hour boil Azidosilane flexural properties flexural properties cone.(wt. percent) in Strength, Modulus, Strength, Modulus, Example No.Azldosilane solvent Solvent p.s.i. p.s.LXlO p.s.i. p.s.i.}(lt) CnnhnlNmm 13, 300 1. 7 9, 800 1.4 532% 3'? 24 583 3% 1 34 81mm? ,700 2.3 27,400 2. 1 .d0 ,200 2.1 24,100 2.1 Methylene chlorlde.. 27, 200 2.4 19,200 2. 3 35 an d0. 39, 900 2. 7 27, 200 2. 6 40, 000 2. 5 31, 000 2. 642, 000 2. 4 24, 500 2. 5

1 Mixed isomers of (trimethoxysilyl)cyclohexylsulionyl aside. 1 Asdescribed in footnote 1 of Example 15.

EXAMPLE 36 The example shows the bonding of a mixture of polypropyleneand poly(vinyl acetate) to samples of glass cloth by treating the saidcloth with an aqueous sizing system containing an azidosilane and adispersion of the polymers,

Control samples were prepared exactly as described above except thepolymers were not first treated with the azidosilane. Samples of thetreated and control laminates were tested for flexural strength andmodulus according to ASTM D-790. The same tests were also conducted onsamples after boiling in water. The results of these tests are set forthin Table VI.

22 EXAMPLE 42 This example shows the bonding of polypropylene to samplesof glass cloth which have first been treated with an aqueous solution ofan azidosilane compound.

Strips of the glass cloth described in Example 18 were immersed in a0.25% by weight aqueous solution of 3- TABLE VI Dry flexural propertiesProperties after boiling in water Treatment of Strength, Modulus, HoursStrength, Modulus, Example No. Polymer polymer p.s.i. p.s.i. 10 boiledp.s.i. p.s.i.X10

7 37 yp py 1 233 3 3; 3?, 1 1 16, 900 2. 1 72 15, 100 1. 6 38Payethylene 13, 200 1. 2 72 8,200 1. 3 39 Poly(ethylene terephthalate-49,400 3.1 24 600 2.3 hexahydroterephthalate) Control 46, 400 2. 8 2412, 000 2.

l Crystalline, having a specific gravity of 0.904 g./cc. and a meltindex of 4 g./10 min. (I2 at 230 0.). I High density, having a specificgravity of 0.952 g./cc. and a melt index of 0.6 g./10 min. (I; at 1900.). Prepared using mole percent dimethylhexahydroterephthalate andhaving a specific viscosity 0.85 at 25 C. in a 60/40 solution of phenoland tetrachloroethane.

EXAMPLE This example shows the bonding of polypropylene to samples ofglass cloth which have first been treated with a diazoacetate silanecompound.

Strips of the glass cloth described in Example 18 were immersed invarious concentrations of 10-[3 (-trimethoxysilylpropyl)carbamoyl] decyldiazoacetate in methylene chloride solution, drained, and hung to dry.The resulting treated glass cloth was used to prepare 12 ply laminateswith crystalline polypropylene film, 5 mils in thickness exactly asdescribed in Example 18. A control sample was prepared in the samemanner except the glass cloth was not first treated with thediazoacetate silane compound. Samples were cut from the treated andcontrol laminates and tested for flexural strength and modulus accordingto ASTM D-790. Tests were also conducted on the samples after boiling inwater. The results of the tests are set forth in Table VII.

(trimethoxysilyl)propylsulfonyl azide, drained and hung to dry. Theaqueous solution had been prepared by adding the sulfonylazide to waterat a pH of 7. The resulting treated glass cloth was used to preparelaminates and tested exactly as described in Example 41. The results ofthe tests are tabulated below:

This example shows the bonding of polypropylene to samples of glasscloth which have first been treated with an azidosilane compound.

TABLE VII Diazoacetete silane Dry flexural 72 hour boil flexuralcompound properties properties cenc. (wt. Percent percent in Strength,Modulus, Strength, Modulus, strength CHzCh p.s.i. p.s.i. l0 p.s.i.p.s.i-XIO' retention 0.500 25,200 1.9 23, 400 1.9 92.7 0. 250 33, 500 2.l 23, 900 2. 1 71. 5 0. 125 33, 300 2. 1 27, 400 2. 2 82. 1 None 12,5001.8 1.4 64.7

EXAMPLE 41 Strips of the glass cloth described in Example 18 were Thisexample shows the bonding of polypropylene to samples of glass clothwhich have first been treated with an azidosilane compound.

Strips of the glass cloth described in Example 18 were immersed in a0.125% by weight solution of mixed isomers of2-(trimethoxysilyl)ethylbenzenesulfonyl azide in benzene, drained, andhung to dry. The resulting treated glass cloth was used to prepare 12ply laminates with crystalline polypropylene film, 5 mils in thicknessexactly as described in Example 18. Control samples were prepared in thesame manner except the glass cloth was not first treated with anazidosilane compound. Samples were cut from the treated and controllaminates and tested for flexural strength and modulus according to ASTMD-790 as described in Examples 31 and 32. The results of the tests aretabulated below:

immersed in a 0.06% by weight solution of N-3-(triethoxysilyl)propyl-N'-3-azidosulfonylphenylurea in benzene, drained, and hung todry. The resulting treated glass cloth was used to prepare laminates andtested exactly as described in Example 41. The results of the tests aretabulated below:

72 hour boil flexural Dry fiexural properties properties Modulus,Modulus, Strength, p.s.i. Strength, p.s.i. p.s.i. X10 p.s.i. X10

Control 12, 500 1. 8 8, 1. 4 Treated 36, 500 2. 0 25, 800 1. 8

EXAMPLE 44 23 thoxysilyl)propyl u-diazo-a-carboethoxy acetate inmethylene chloride. The thus treated felts were dried and then laid upto form the laminate by alternating plies of the treated asbestos feltand sheets of the polypropylene film. The resulting assembly wascompression molded at a temperature of 220 C. for 7 minutes at contactpressure, 3 minutes at a pressure of 440 p.s.i. and then cooled to 23 C.under 440 p.s.i. pressure to form a /8 inch thick laminate. A controllaminate was prepared exactly as described above except the treatmentwith the diazosilane was omitted. Samples were cut from the treated andcontrol laminates and tested for flexural strength and modulus accordingto ASTM D-790. The results of the tests are tabulated below:

Flexural Flexural strength, modulus p.s.i. X10 (p.s.i.)

Control 15, 900 0. 9 Treated 18, 900 1.

EXAMPLE 45 This example shows the bonding of polypropylene to samples ofasbestos felt which have first been treated with an azidosilanecompound.

Strips of the asbestos felt described in Example 44 were immersed in a0.4% by weight solution of 3-(trimethoxysilyl)-propylsulfonyl azide inmethylene chloride and dried. The resulting treated felt was used toprepare laminates with crystalline polypropylene and tested exactly asdescribed in Example 44. The results of the tests are tabulated below:

Flpxural Flexural strength, modulus p.s.t. X (p.s.i.)

crmh-nl 15, 900 0- 9 Treated 19, 500 1. 1

EXAMPLE 46 TABLE VH1 72 hour boll fiexural Diazosilane Dry flexuralproperties properties oonc. (wt.

percent) in Strength, Modulus, Strength, Modulus, Sample CH2C12 p.s.i.p.s.i. 10 p.s.i. p.s.i. (10

Cont 1... None 13, 300 1. 7 8,900 1. 2 B- 0.062 24,000 1. 8 12, 200 1.7b- 0. 125 26, 900 1. 9 16, 200 1. 7 c. 0. 25 25, 200 1. 8 16, 700 1. 7.d 0. 50 30, 200 2. 1 17, 500 1. 9

EXAMPLE 47 This example shows the bonding of polypropylene to samples ofglass cloth which have first been treated with a diazosilane compound.

The procedure used in this example is the same as that described inExample 46 except the glass cloth was immersed in a 0.25% by weightdispersion of the diazosilane compound in water at a pH of 4-5. Theresulting lami- 24 nates were treated as described in Example 18. Theresults of the tests are tabulated below:

This example shows the bondingof polyester tire cord to rubber tirestock using an azidosilane compound.

Poly(ethylene terephthalate) tire cord 1,000 denier and 3 ply, underabout 500 grams of tension was passed twice through a trough contaianinga 5% solution of 3-(trimethoxysilyl)-propyl azidoformate in a mixedtrichloroethylene-methylene chloride solvent. The cord was next passedthrough two ovens in series at 200 F. and 400 F. Residence times in theovens was 65 and 54 seconds respectively. The cord dip pick-up wasapproximately 1.4% by weight.

The modified cord was next dipped in a resin latex prepared as follows:To a solution of 0.24 part of sodium hydroxide in 192.8 parts of waterwas added 8.8 parts of resorcinol with continued stirring until acomplete solution was achieved. Then 12.2 parts of 37% formaldehyde wasadded. The solution was aged for approximately 5 hours at about 75 C.and then added slowly to a mixture of 48 parts water and parts of acommercial latex, comprising a 41% solids terpolymer of styrene,butadiene and vinylpyridine. The monomers being present in a ratio ofapproximately 15:70:15. The mixture was stirred slowly for 15 minutesand its pH adjusted to 10.3 using concentrated ammonium hydroxide. Theresulting gray-violet latex contained approximately 20% solids. Theazidosilane treated cord was passed twice through a trough of the abovedescribed tire cord coating under a tension of 500 grams and then driedand cured for 54 seconds at a temperature of 430 F.

The thus coated cord was then embedded in a vulcanizable rubber tirestock and cured in the form of inch The test specimens were cured for 45minutes at a temperature of 307 F. After several hours conditioning atroom temperature the H-specimens were tested according to the procedureof ASTM D-2l38-62T. An average (6 test specimens) of 29 pounds wererequired to overcome the tire-cord rubber adhesion. A control specimentreated exactly the same as above except for the azidosilane treatmentgave an average of 17 pounds required to overcome the tire cord-rubberadhesion. A specimen treated with the azidosilane as described above butnot treated with the resorcinol-formaldehyde latex dip gave an averagevalue between that reported for the test specimens and that reported forthe control specimens.

EXAMPLE 49 Glass tire cord was bonded to rubber tire stock exactly asdescribed in Example 48 with the exception of heating the cord after ithad been passed twice through the trough containing the solution of3-(trimethoxysilyljppropyl azido- This example shows the bonding ofpolyester fabric to silicone rubber using an azidosilane compound.

Woven poly(ethylene terephthalate) fabric weighing 4 ounces per squareyard was dipped into a 24% solution of 2-chloro-3- [3-(trimethoxysilyl)propoxy] propyl azidoformate in methylene chloride, air dried, and thenbaked in an air oven for 1 hour at a temperature of 150 C. The thustreated fabric was plyed with 0.04 inch sheets of silica filled, vinylsubstituted silicon rubber, containing 0.5% by weight of benzoylperoxide, forming a sandwich-like structure having polyester fabric onthe top and bottom with two sheets of silicon rubber in-between. Theresulting structure was placed in a rubber press, equipped with spacersto hold the plates 0.072 inch apart. The structure was then cured for 45minutes under pressure at a temperature of 110 F. The resulting laminatewas tested to determine the force required to separate the fabric fromthe the rubber. In T-peel tests carried out at 2 inches per minute therubber failed rather than separating from the fabric (requiring a loadof 45 lbs./in.). A control sample not treated with the azidosilaneseparated from the rubber at about 6 lbs/in.

EXAMPLE 51 This example shows the bonding of polyester fabric tosilicone rubber using an azidosilane compound.

Woven poly(ethylene terephthalate) fabric weighing 4 ounces per squareyard was dipped into a 22% solution of2-(trimethoxysilyl)ethylbenzenesulfonyl azide in methylene chloride, airdried, and then baked in an air oven for 1 hour at a temperature of 177C. The fabric was then dipped into a 5% solution of vinyltriethoxysilanein tetrachloroethylene, air dried, and baked in an air oven for 20minutes at a temperature of 150 F. The thus treated fabric was plyedwith 0.04 inch sheets of silica filled, vinyl substituted siliconrubber, containing 0.5% by weight of benzoyl peroxide, forming asandwich-like structure, cured and tested as described in Example 50. In

26 F., and the mold was heated to 120 F. The resulting test specimenshad a 30% higher fiexural modulus at 1% strain and 15% more flexuralstrength after exposure to boiling water for 72 hours than controlmoldings made the same way using untreated glass beads.

EXAMPLE 5 3 This example shows the use of an azidosilane compound tosize glass rovings.

An aqueous solution of 0.5 by weight 2-(trimethoxysilyl)ethylbenzenesulfonyl azide and 0.25% by weight watersoluble epoxy resin, having an epoxide equivalent weight of 117, wasapplied to continuous rovings of electrical glass fi-bers as they wereformed at the glass drawing bushing. The thus sized rovings were takenup on a spool, baked for 40 minutes at a temperature of 100 C., and thenchopped into A inch lengths. The chopped rovings were blended with thecrystalline polypropylene described in Example 52 to provide a glasslevel of 30% by-weight. The mixture was fed into a reciprocating screwinjection molding machine maintained at 440 F. in zone 1, 460 F. in zone2, 470 F. at the nozzle and the mold heated to 120 F. The /2 by A; by 5inch specimens were tested and found to have a flexural strength of15,000 p.s.i. Control specimens, not treated with the azidosilanecompound had a fiexural strength of 9,000 p.s.i. In addition to thedifference in strength the treated rovings were much easier to handle inthat they maintained their intergn'ty to a much greater extent than theuntreated rovings.

EXAMPLES 54 AND 55 These examples show the bonding of polymers to glasscloth which has been treated with an azidosilane compound.

Strips of the glass cloth described in Example 18 were immersed in a0.37% by weight solution of Z-(trimethoxysilyl)ethylbenzenesulfonylazide in methylene chloride, drained, and hung to dry. The resultingtreated glass cloth was used to prepare 12 ply laminates with 2diiferent polymers as described in Example 18. Control samples wereprepared exactly as described above except the glass cloth was not firsttreated with the azidosilane compound. Sam ples of the treated andcontrol laminates were tested as described in Examples 19-30. Thepolymers used and T-peel tests the rubber failed rather than separatingfrom the results of the tests are tabulated below:

Dry fiexural 72 hour boil properties fiexural properties Strength,Modulus, Strength Modulus,

Example Polymer p.s.1. p.s.i.X10 p.s.i p.s.i. 10

54 Polyethylene 35, 600 2. 2 28,400 2. 2 Control 11, 900 1. 5 7, 400 0.8Polyhutenel 24, 150 1 6 10,600 1.2 Control-..- 11,000 1 5 7,000 1.0

1 High density, havin a s eeifie avit of 0.952 cc. and a melt index i4.6 10 i (patmooc) g p E y 0 s/ mu 2 Isotactic sold under the trade name"Vestolen BT-1711."

the fabric. A control sample not treated with the azidosilane separatedfrom the rubber at about 6 lbs/in.

EXAMPLE 52 This example shows the use of an azidosilane compound toimprove the physical properties of glass bead filled polypropylene.

Glass beads ranging in size from about 6 to 44 microns and having aspecific gravity of 2.48 grams/cc. were dipped into a methanol solutionof Z-(trimethoxysilyl)ethylbenzenesulfonyl azide. The beads were dried,leaving about 0.2% by weight pick-up of azidosilane compound. The thustreated beads were dry blended in a mill with crystalline polypropylenehaving a melt index (I at 230 C.) of 14 g., in a ratio of 30 parts ofbeads to 70 parts of polymer by weight. The mixture was then screwinjectionmolded to form test specimens /2 by /8 by 5 inches in size.Zone 1 of the injection molding machine was main- I claim: 1. A nitrogencontaining silane compound having the where R is selected from the groupconsisting of alkylene, cycloalkylene, alkylene substitutedcycloalkylene, arylene, alkylene substituted arylene, alkylenediarylene, alkyleneoxy-alkylene, arylene-oxy-arylene,alkylenearylene-oxyarylene, alkylenearylene-oxy-alkylenearylene,arylenealkylene-oxy-alkylene, arylenealkylene-oxy arylenealkylene,alkylene-thio-alkylene, arylene-thio-arylene,arylenealkylene-thio-arylenea1kylene, alkylene-sulfonyl-alkylene,arylene-sulfonyl-arylene, alkylenearylene-sulfonyl-arylene,alkylenearylene-sulfonyl alkylenearylene, alkylenearylenetained at 440E, Zone 2 at 460 F the nozzle at 470 sulfonylalkylene, arylenealkylenesulfonyl-arylenealkyl- 2 v ene, and the corresponding halogenatedradicals; X is a radical selected from the group consisting of halo,hydroxy, alkoxy, aryloxy, -N -NH alkyl substituted amine, amide andorgano oxycarbonyl radicals selected from alkyl oxycarbonyl, cycloalkyloxycarbonyl and aryl oxycarbonyl radicals; T is a radical selected fromthe group consisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkylradicals; a is an integer from 1 to 3; b is an integer from 0 to 2; c isan integer from 1 to 10; d is an integer from 1 to 3; and a-i-bH-cequals 4; wherein the said arylene and aryl radicals are carbocyclicarylenes and aryis, respectively, containing 6 to 18 carbon atoms, thesaid alkylene and alkyl radicals contain 1 to 20 carbon References CitedUNITED STATES PATENTS 3,466,314 9/1969 Moedritzer et a1; 260-349 JOHN M.FORD, Primary Examiner US. Cl. X.R.

260448.2 N, 29.2 N; l17123 D; 156-326; 161-493 3 3 UNITED STATES PATENTOFFICE CERTIFICATE OF CORRECTION Patent No. U.S.P.' Dated December 12,197 2 Inventor(s) J. Brent Thomson (Case Z; 3-6

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby correctedas shown below:

Col. 1, Line 35 "1964" should read "1969" Col. 7, Line 24 ilr kage"should read "linkage" Col. 18, Table III, Example 25 under Strength,psi"9,10" should read "9, 100" Col. 26, Line 28 and 29 "intergrity" shouldread "integrity" Signed and sealed this 1st day of May 1973.

EDWARD M. FLETCHER, JR. ROBERT GOTTSCHALK Commissioner of PatenisAttesting Officer

